WO1994004372A1 - Feuille de colorant pour impression par transfert thermique - Google Patents

Feuille de colorant pour impression par transfert thermique Download PDF

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Publication number
WO1994004372A1
WO1994004372A1 PCT/GB1993/001819 GB9301819W WO9404372A1 WO 1994004372 A1 WO1994004372 A1 WO 1994004372A1 GB 9301819 W GB9301819 W GB 9301819W WO 9404372 A1 WO9404372 A1 WO 9404372A1
Authority
WO
WIPO (PCT)
Prior art keywords
dye
sheet according
polymer
formula
parahydroxystyrene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB1993/001819
Other languages
English (en)
Inventor
Andrew Trevithick Slark
David Wood Jarvis
Akihiro Kawamura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Priority to DE69314958T priority Critical patent/DE69314958T2/de
Priority to JP6506085A priority patent/JPH08500542A/ja
Priority to EP94908084A priority patent/EP0656834B1/fr
Priority to US08/387,841 priority patent/US5565406A/en
Publication of WO1994004372A1 publication Critical patent/WO1994004372A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
    • B41M5/395—Macromolecular additives, e.g. binders
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate

Definitions

  • This invention relates to a thermal transfer printing (TTP) dye sheet, in particular to a dye sheet having an improved dye binder.
  • TTP thermal transfer printing
  • Thermal transfer printing is a printing process in which a dye is caused, by thermal stimuli, to transfer from a dye sheet to a receiver sheet thereby to form an image on the receiver sheet.
  • the dye sheet and receiver sheet are placed in intimate contact, the thermal stimuli are applied to the dye sheet to cause dye transfer and the dye sheet and receiver sheet are then separated.
  • the thermal stimuli may be provided by a programmable print head which is in contact with the dye sheet or by for example, a laser in a light-induced thermal transfer process ( ITT).
  • Dye-sheets conventionally comprise a substrate having on ' one surface thereof a dye coat which typically comprises a thermally transferable dye dispersed or dissolved in a binder.
  • Dye-sheets may also comprise a backcoat to impart desirable properties for example, good handling and thermal characteristics to the dye sheet.
  • a primer or subbing layer may be employed between the substrate and the dye coat and/or the substrate and the backcoat for example to improve the adhesion of the coat to the substrate.
  • J59199295 discloses an ink composition for sublimation transfer which consists of cellulose acetate, polystyrene, a disperse dye, silica and methylethyl ketone.
  • a first aspect of the invention provides a thermal transfer printing dye sheet which comprises a substrate having on one side, a dye coat comprising a binder and a thermally transferable dye wherein the binder comprises a mixture of a cellulosic polymer and a second polymer having, as at least 102 of the monomeric units of the polymer, a monomeric unit of formula (I);
  • X is H or methyl and Y is an optionally substituted phenyl group, a cyano group or an ester group of formula -CO2Z wherein Z is an optionally substituted C_ to C5 hydrocarbyl group with the proviso that where Y is an unsubstituted phenyl group the second polymer also has a substituted styrene and/or a non-styrene monomeric unit.
  • Dye-sheets according to the present invention have been found to exhibit a particularly advantageous combination of characteristics.
  • good resistance to low temperature thermal transfer may be achieved which provides for improved image quality and images may be produced which have excellent optical density.
  • the second polymer may be a homopolymer, the monomeric unit of which is derived from parahydroxystyrene, the phenyl group of which may or may not be further substituted.
  • the second polymer may be a copolymer (block, random, alternating or graft) and formed of monomeric units according to formula 1 where Y is substituted phenyl and monomeric units according to formula 1
  • Y is unsubstituted phenyl or an ester group of formula -CO2Z where Z is an optionally substituted ⁇ ⁇ to CQ hydrocarbyl group, and/or monomeric units derived from maleic anhydride.
  • the second polymer may be a copolymer formed of monomeric units according to formula 1 where Y is unsubstituted phenyl and monomeric units derived from maleic anhydride.
  • the second polymer may be a copolymer formed of monomeric units according to formula 1 where Y is unsubstituted phenyl and monomeric units according to formula 1 where Y is an ester group of formula
  • Z is an optionally substituted Ci to Cs hydocarbyl group.
  • the further substituent on the phenyl group is halogen (most preferably bromine), glycidyl neodecanoate, hydroxymethyl, dimethylaminomethyl, 2-hydroxyethylmethylaminomethyl, t-butyl, sulphonate, styrene or benzoate.
  • the hydocarbyl group is hydroxyethyl, hydroxypropylor hydroxybutyl.
  • a most preferred thermal transfer printing dye sheet comprises a substrate having on one side, adye coat comprising a binder and a thermally transferable dye wherein the binder comprises a mixture of a cellosic polymer and a second polymer selected from the group consisting of : a parahydroxystyrene homopolymer, a bromo-parahydroxystyrene homopolymer, a coplymer of parahydroxystyrene and parahydroxystyrene further substituted with halogen( eg bromine), glycidylneodecanoate, hydroxymethyl, dimethylaminomethyl, 2-hydroxyethylmethylaminomethyl, t-butyl, sulphonate, styrene or benzoate, a coplymer of parahydroxystyrene with or without a further substituent on the phenyl group and any one or a mixture of methyl (meth)acrylate,
  • the second polymer is a copolymer
  • at least 10Z and preferably at least 25Z of the monomeric units of the polymer, based on the total number of monomeric units in the polymer are of formula (I).
  • the two monomeric units are suitably present in a ratio in the range 15:85 to 85:15 and preferably 25:75 to 75:25.
  • the glass transition temperature (Tg) of the second polymer is suitably in the range 50 to 200°C and preferably 60 to 185°C.
  • a further aspect of the invention provides a thermal transfer printing method which comprises placing a dye-sheet according to any aspect of the present invention in contact with a receiver sheet which comprises a substrate having on one side a dye-receptive surface, applying thermal stimuli to the dye-sheet at pre-determined locations to effect thermal transfer of the dye from the said locations to the dye-receptive surface thereby to form a pre-determined dye image and separating the dye-sheet and the receiver sheet.
  • the cellulosic polymer is an optionally substituted alkyl cellulose for example ethyl cellulose, hydroxyethyl cellulose, ethylhydroxy cellulose, ethylhydroxyethyl cellulose and hydroxypropyl cellulose or any suitable mixture thereof.
  • Other cellulosic polymers may be employed if desired for example nitro cellulose.
  • the cellulosic polymer has a molecular weight (Mw) of 50000 to 260000.
  • Both the cellulosic polymer and the second polymer are suitably present in the dye sheet binder composition in an amount of at least ⁇ 1 by weight of the total binder.
  • the binder comprises the cellulosic polymer and the second polymer in a weight ratio of 95:5 to 5:95 and more preferably in a ratio of 85:15 to 15:85.
  • the dyecoat is formed by coating the substrate, or a layer on the substrate, with an ink prepared by dissolving or dispersing one or more thermal transfer dyes and the binder in a liquid vehicle to form a coating composition; then removing any volatile liquids. Any dye capable of being thermally transferred in the manner described above, may be selected as required.
  • Dyes known to thermally transfer come from a variety of dye classes, e.g. from such nonionic dyes as azo dyes, anthraquinone dyes, azomethine dyes, methine dyes, indoaniline dyes, naphthoquinone dyes, quinophthalone dyes and nitro dyes.
  • the ink may also include dispersing agents, antistatic agents, antifoaming agents, and oxidation inhibitors, and can be coated onto the substrate as described for the formation of the latter.
  • the thickness of the dyecoat is suitably 0.1-5 ⁇ m, preferably 0.5-3 ⁇ _m.
  • the dye and binder are suitably present in the dye-coat in a weight ratio of 0.1 to 3:1 of dye to binder.
  • the relative amounts of dye and binder are suitably selected depending on the particular dye and binder employed and the application for which the dye sheet is to be used.
  • the dye sheet comprises a backcoat disposed on the opoosite side of the substrate to the dye-coat to provide suitable heat resistance and slip and handling properties.
  • Suitable backcoats having a desirable balance of proerties include those described in EP-A-314348 and especially those described in EP-A-458522.
  • Particularly preferred backcoats include those in which the backcoat comprises the reaction product of radically co-polymerising in a layer of coating composition, the following constituents: a) at least one organic compound having a plurality of radically poly erisable saturated groups per molecule and b) at least one organic compound having a single rradicallty polymerisable unsaturated group the backcoat also containing an effective amount, as slip agent, of c) a metallic salt of a phosphate ester.
  • a light absorbing material may be included in the dye-coat or, if desired, a separate absorber layer comprising a light absorbing material disposed between the dye-coat and the substrate may be employed.
  • the light-absorbing material suitably comprises a material which is an absorber for the inducing light to convert it into the required thermal energy to effect transfer of the dye.
  • the absorber is preferably carbon black, as this provides good absorption and conversion to heat, of a broad spectrum of wavelengths, and hence is not critical to the inducing light source employed for the printing, further, it is also relatively cheap.
  • any suitable absorber matereials known in the art may be employed as desired.
  • organic materials known to absorb at the laser wavelengths. Examples of such materials include the substituted phthalocyanines described in EP-B-157,568, which can readily be selected to match laser diode radiation at 750-900 nm, for example.
  • a variety of materials can be used for the substrate, including transparent polymer films of polyesters, polyamides, polyimides, polycarbonates, polysulphones, polypropylene and cellophane, for example.
  • Biaxially orientated polyester film is the most preferred, in view of its mechanical strength, dimensional stability and heat resistance,.
  • the thickness of the substrate is suitably 1-50 ⁇ m, and preferably 2-30 ⁇ m.
  • Various coating methods may be employed to coat the dye-coat and if present, other coats for example a backcoat, onto the substrate, including, for example, roll coating, gravure coating, screen coating and fountain coating.
  • the coating can be cured by heating or by irradiating with electromagnetic radiation, such as ultraviolet light, electron beams and gamma rays, as appropriate.
  • electromagnetic radiation such as ultraviolet light, electron beams and gamma rays, as appropriate.
  • Typical curing conditions are heating at 50-150°C for 0.5-10 minutes (in the case of thermal curing), or exposure to radiation for 1-60 s from an ultraviolet lamp of 80 W/cm power output, positioned about 15 cm from the coating surface (in case of ultraviolet light curing).
  • In-line UV curing may utilise a higher powered lamp, eg up to 120 W/cm power output, focused on the coating as it passes the lamp in about 0.1-10 ms.
  • the coating is preferably applied with a thickness such that after drying and curing the thickness is 0.1-5 ⁇ m, preferably 0.2-3 ⁇ m, and will depend on the concentration of the coating composition.
  • the dye sheet may be elongated in the form of a ribbon and housed in a cassette for convenience, enabling it to be wound on to expose fresh areas of the dyecoat after each print has been made.
  • Dyesheets designed for producing multicolour prints have a plurality of panels of different uniform colours, usually three: yellow, magenta and cyan, although the provision of a fourth panel containing a black dye, has also previously been suggested.
  • these different panels When supported on a substrate elongated in the form of a ribbon, these different panels are suitably in the form of transverse panels, each the size of the desired print, and arranged in a repeated sequence of the colours employed.
  • panels of each colour in turn are held against a dye-receptive surface of the receiver sheet, as the two sheets are imagewise selectively irradiated to transfer the dye selectively where required, the first colour being overprinted by each subsequent colour in turn to make up the full colour image.
  • a selection of dye sheets were produced by coating a dye coat of composition listed in Table 1 onto a 6 ⁇ m thick polyethylene terephthalate substrate having a subcoat (onto which the dye coat was coated) on one side and a backcoat on the opposite side using a wire bar. For all the dye sheets the substrate, sub coat and backcoat were the same. Once coated, the dye coat was dried in an oven for 20 seconds a 110°C to produce a dye sheet having a dry dye coat thickness of l ⁇ m. Examples IB, 1C, ID, IF and 1G
  • Examples IA and IE are comparative Examples according to the prior art.
  • Cl was 3-acetylamino-4-(3-cyano-5-phenylazothiophenyl-2-ylazo)-N,N-diethyl aniline; C2 was Cl solvent blue 63; M0 was Cl disperse red 60; M3 was
  • Ethyl cellulose was grade ECT-10 available from Hercules;
  • LYNCUR MB was a brominated pol (parahydroxystyrene)
  • LYNCUR PHMC was a poly(parahydroxystyrene)
  • LYNCUR CMM was a copolymer of parahydroxystyrene and methyl methacrylate all available from Maruzen;
  • SYNTHACRYL was a styrene/acrylate copoloymer available from Hoechst.
  • a receiver sheet was produced by coating onto a polyethylene terephthalate substrate having a backcoat and a subcoat, a dye-receptive layer of the following composition;
  • the dye-receptive coat was dried for 3 minutes at 140°C to provide a dry coat thickness of 4 ⁇ m.
  • Example 2 The dye sheets produced in Example 1 were each brought into contact with a sample of the receiver sheet and thermal transfer printing was effected by means of a programmable print head supplying heat pulses of 2 to 14 millisecond duration to the backcoat of the dye sheet to provide a gradation in the optical density of the print image.
  • the dye sheet and receiver sheet were separated following printing and the reflection optical densities on the receiver sheet were measured using a Sakura densitometer and are shown in Table 2.
  • Example 3 Example 3
  • samples of the dye sheets produced in Example 1 and the receiver sheet produced in Example 2 were fed, in register, through a 2-roll laminator (OZATEC HRL350 hot roll laminator available from Hoechst) at 0.2 ms -1 .
  • the rolls of the laminator were maintained at a temperature of 60°C and the pressure between them was 5 bar.
  • the reflection optical densities on the receiver sheet were measured using a Sakura densitometer and are shown in Table 2, the column headings denoting which dye sheet was used in the test.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Abstract

Feuilles de colorant pour impression par transfert thermique, comprenant une couche de colorant contenant un liant composé d'un polymère cellulosique et d'un second polymère dont au moins 10 % des unités monomères répondent à la formule (I): -[H2C-CXY]-, dans laquelle X représente H ou méthyle et Y représente un groupe phényle éventuellement substitué, un groupe cyano ou un groupe ester de la formule -CO2Z, Z représentant un groupe hydrocarbyle C1 à C6 éventuellement substitué, à condition que, lorsque Y représente phényle, le second polymère comprenne également une unité monomère styrène et/ou non-styrène substituée.
PCT/GB1993/001819 1992-08-26 1993-08-26 Feuille de colorant pour impression par transfert thermique Ceased WO1994004372A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE69314958T DE69314958T2 (de) 1992-08-26 1993-08-26 Thermische farbstoffübertragungsdruckschicht
JP6506085A JPH08500542A (ja) 1992-08-26 1993-08-26 熱転写印刷用染料シート
EP94908084A EP0656834B1 (fr) 1992-08-26 1993-08-26 Feuille de colorant pour impression par transfert thermique
US08/387,841 US5565406A (en) 1992-08-26 1993-08-26 Thermal transfer printing dye sheet

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9218184.1 1992-08-26
GB929218184A GB9218184D0 (en) 1992-08-26 1992-08-26 Thermal tansfer printing dye-sheet

Publications (1)

Publication Number Publication Date
WO1994004372A1 true WO1994004372A1 (fr) 1994-03-03

Family

ID=10721016

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1993/001819 Ceased WO1994004372A1 (fr) 1992-08-26 1993-08-26 Feuille de colorant pour impression par transfert thermique

Country Status (6)

Country Link
US (1) US5565406A (fr)
EP (1) EP0656834B1 (fr)
JP (1) JPH08500542A (fr)
DE (1) DE69314958T2 (fr)
GB (1) GB9218184D0 (fr)
WO (1) WO1994004372A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7666815B2 (en) * 2004-12-20 2010-02-23 Eastman Kodak Company Thermal donor for high-speed printing
US7273830B2 (en) * 2004-12-20 2007-09-25 Eastman Kodak Company Thermal donor for high-speed printing

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59199295A (ja) * 1983-04-28 1984-11-12 Sony Corp 昇華転写式コピ−用インキリボンのインキ組成物
JPS61692A (ja) * 1984-06-12 1986-01-06 尾池工業株式会社 昇華性捺染転写箔
US4946826A (en) * 1988-07-20 1990-08-07 Victor Company Of Japan, Ltd. Thermal transfer sheet comprising an improved ink layer
EP0469723A1 (fr) * 1990-07-30 1992-02-05 Imperial Chemical Industries Plc Impression par tranfert thermique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59199295A (ja) * 1983-04-28 1984-11-12 Sony Corp 昇華転写式コピ−用インキリボンのインキ組成物
JPS61692A (ja) * 1984-06-12 1986-01-06 尾池工業株式会社 昇華性捺染転写箔
US4946826A (en) * 1988-07-20 1990-08-07 Victor Company Of Japan, Ltd. Thermal transfer sheet comprising an improved ink layer
EP0469723A1 (fr) * 1990-07-30 1992-02-05 Imperial Chemical Industries Plc Impression par tranfert thermique

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 102, no. 20, 20 May 1985, Columbus, Ohio, US; abstract no. 176597p, SONY CORP.: "Ink composition for ink ribbon used in sublimation transfer copying." page 657; column LEFT; *
DATABASE WPI Week 8607, Derwent World Patents Index; AN 86-046114 *
PATENT ABSTRACTS OF JAPAN vol. 9, no. 67 (M - 366) 27 March 1985 (1985-03-27) *

Also Published As

Publication number Publication date
DE69314958T2 (de) 1998-03-26
GB9218184D0 (en) 1992-10-14
DE69314958D1 (de) 1997-12-04
EP0656834B1 (fr) 1997-10-29
US5565406A (en) 1996-10-15
JPH08500542A (ja) 1996-01-23
EP0656834A1 (fr) 1995-06-14

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